Methods of growing nitride semiconductors and methods of manufacturing nitride semiconductor substrates

ABSTRACT

Methods of growing nitride semiconductor layers including forming nitride semiconductor dots on a substrate and growing a nitride semiconductor layer on the nitride semiconductor dots. The nitride semiconductor layer may be separated from the substrate to be used as a nitride semiconductor substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. 119 to Korean PatentApplication No. 10-2010-0015247, filed on Feb. 19, 2010, and KoreanPatent Application No. 10-2010-0082085, filed on Aug. 24, 2010 in theKorean Intellectual Property Office (KIPO), the entire contents of eachof which are incorporated herein by reference.

BACKGROUND

1. Field

Example embodiments relate to methods of growing nitride semiconductorlayers and nitride semiconductor substrates manufactured using themethods.

2. Description of the Related Art

Electronic industries using nitride semiconductors have been consideredas suitable fields for developing and growing green industries. In oneexample, Gallium nitride (GaN) is widely used as a nitride semiconductorin fabrication of blue light-emitting diodes. Blue light-emitting diodesare a core component of high-power electronic devices. High-powerelectronic devices commonly include red, green, and/or bluelight-emitting diodes (LED) as core components. A blue LED fabricatedwith GaN has improved brightness, lifespan, and internal quantumefficiency compared to the conventional blue light-emitting devicefabricated with Zinc selenide (ZnSe) due to the better physical andchemical properties of the GaN. The GaN has a direct transition bandgapstructure and the bandgap is adjustable from about 1.9 to about 6.2 eVby using an alloy such as Indium or Aluminum. Therefore, GaN may be usedfor light devices. In addition, GaN has a relatively high breakdownvoltage and is more stable at higher temperatures and may be used invarious fields such as higher power devices and higher temperatureelectronic devices. For example, GaN may be applied in large electronicsigns using full-color displays, traffic lights, light sources ofoptical recording media, high power transistors for vehicle engines andthe like. A LED fabricated using a GaN substrate has less defects, thesame or substantially the same refractive index in both the GaNsubstrate and the device layer, and a thermal conductivity that is aboutfour-times greater than that of sapphire (Al₂O₃). Thus, GaN is usedfrequently in fabricating higher power LEDs.

SUMMARY

Provided are methods of growing semiconductor layers and methods ofmanufacturing semiconductor substrates. Cracks and/or dislocations maybe generated while growing a semiconductor layer due to the strain oninterfaces caused by the difference between lattice constants and/orthermal expansion coefficients of the semiconductor layer and asubstrate. A nitride semiconductor layer grown according to exampleembodiments may be crack free and/or a crack free thickness of thenitride semiconductor layer may be increased. A dislocation density ofthe semiconductor layer may be reduced.

According to example embodiments, a method of growing a nitridesemiconductor layer includes preparing a substrate, forming nitridesemiconductor dots on the substrate and growing a nitride semiconductorlayer on the nitride semiconductor dots.

The method may further include forming a stress relaxation layer inwhich the nitride semiconductor dots are connected to each other duringgrowing of the nitride semiconductor layer. The nitride semiconductorlayer may have a thickness that is equal to or greater than a thicknessof the stress relaxation layer. A thickness of the stress relaxationlayer may be about 1 μm to 100 μm. The nitride semiconductor layer maybe formed by using a halide vapor phase epitaxy (HVPE) method. Thenitride semiconductor dots may be formed in-situ when the nitridesemiconductor layer is grown on the substrate by using the HVPE method.The nitride semiconductor dots may be arranged in a direction. Athickness of the grown nitride semiconductor layer may depend on anaverage size of the nitride semiconductor dots.

The nitride semiconductor dots may mostly have an average size of about0.4 μm or greater. The nitride semiconductor dots may mostly have anaverage size of about 0.4 μm to about 0.8 μm. Here, the thickness of thegrown nitride semiconductor layer may be about 100 μm to about 1000 μm.The nitride semiconductor dots may mostly have an average size of about0.4 μm or less. Here, the thickness of the grown nitride semiconductorlayer may be about 10 μM or less. The nitride semiconductor layer andthe nitride semiconductor dots may include gallium nitride (GaN). Thenitride semiconductor dots may have hexagonal shapes. The substrate maybe a sapphire substrate. The nitride semiconductor layer may beseparated from the substrate by a laser liftoff method to be used as anitride semiconductor substrate. The nitride semiconductor substrate maybe a GaN substrate. The nitride semiconductor dots may be on a surfaceof the nitride semiconductor layer.

According to other example embodiments, a nitride semiconductorsubstrate includes nitride semiconductor dots and a nitridesemiconductor layer grown on the nitride semiconductor dots.

The nitride semiconductor substrate may further include a stressrelaxation layer in which the nitride semiconductor dots are connectedto each other during growing of the nitride semiconductor layer. Thenitride semiconductor layer may have a thickness that is equal to orgreater than a thickness of the stress relaxation layer. A thickness ofthe stress relaxation layer may be about 1 μm to 100 μm. The nitridesemiconductor dots may be arranged in a direction on a surface of thenitride semiconductor layer. The nitride semiconductor dots may mostlyhave an average size of about 0.4 μM to about 0.8 μm. The thickness ofthe grown nitride semiconductor layer may be about 100 μm to about 1000μm. The nitride semiconductor dots may mostly have an average size ofabout 0.4 μm or less. The thickness of the grown nitride semiconductorlayer may be about 10 μm. The semiconductor dots may have hexagonalshape on a surface of the nitride semiconductor layer.

According to still other example embodiments, a method of growing anitride semiconductor layer includes forming a plurality of nitridesemiconductor dots on a substrate and growing a nitride semiconductorlayer on the nitride semiconductor dots. According to yet other exampleembodiments, a method of manufacturing a material layer includes growinga plurality of cores on a first layer including a first material,growing a second layer including at least one second material from thecores and growing a third layer including at least one third material onthe second layer, the first material different from the third material.According to further example embodiments, a nitride semiconductorsubstrate includes a plurality of nitride semiconductor dots and anitride semiconductor layer on the nitride semiconductor dots. Accordingto still further example embodiments, semiconductor substrate includes afrontside substrate layer and a backside substrate layer including aplurality of material dots.

BRIEF DESCRIPTION OF THE DRAWINGS

Example embodiments will be more clearly understood from the followingbrief description taken in conjunction with the accompanying drawings.FIGS. 1-6 represent non-limiting, example embodiments as describedherein.

FIG. 1 is a cross-sectional diagram illustrating methods of growing asemiconductor layer on a substrate according to example embodiments;

FIG. 2 is a cross-sectional diagram of a semiconductor layer separatedfrom a substrate;

FIG. 3 is a perspective diagram of semiconductor dots formed on asubstrate;

FIG. 4A is a scanning electron microscope (SEM) image of ALN nanodots ona sapphire substrate;

FIGS. 4B and 4C are scanning electron microscope (SEM) images showingGaN dots grown on a sapphire substrate;

FIG. 5 is an optical microscope image showing a stress relaxation layerformed between GaN dots used as cores on a sapphire substrate, and a GaNlayer on the GaN dots and the stress buffer layer; and

FIG. 6 is an optical image showing thick GaN/sapphire layers grownaccording to example embodiments with diameters of about 3 inches andabout 4 inches.

It should be noted that these figures are intended to illustrate thegeneral characteristics of methods, structure and/or materials utilizedin certain example embodiments and to supplement the written descriptionprovided below. These drawings are not, however, to scale and may notprecisely reflect the precise structural or performance characteristicsof any given embodiment, and should not be interpreted as defining orlimiting the range of values or properties encompassed by exampleembodiments. For example, the relative thicknesses and positioning ofmolecules, layers, regions and/or structural elements may be reduced orexaggerated for clarity. The use of similar or identical referencenumbers in the various drawings is intended to indicate the presence ofa similar or identical element or feature.

DETAILED DESCRIPTION

Various example embodiments will now be described more fully withreference to the accompanying drawings in which some example embodimentsare shown. Example embodiments may, however, be embodied in manydifferent forms and should not be construed as being limited to theembodiments set forth herein; rather, these embodiments are provided sothat this disclosure will be thorough and complete, and will fullyconvey the concept of example embodiments to those of ordinary skill inthe art. In the drawings, the thicknesses of layers and regions may beexaggerated for clarity. Like reference numerals in the drawings denotelike elements, and thus their description will be omitted.

It will be understood that when an element is referred to as being“connected” or “coupled” to another element, it can be directlyconnected or coupled to the other element or intervening elements may bepresent. In contrast, when an element is referred to as being “directlyconnected” or “directly coupled” to another element, there are nointervening elements present. Like numbers indicate like elementsthroughout. As used herein the term “and/or” includes any and allcombinations of one or more of the associated listed items. Other wordsused to describe the relationship between elements or layers should beinterpreted in a like fashion (e.g., “between” versus “directlybetween,” “adjacent” versus “directly adjacent,” “on” versus “directlyon”).

It will be understood that, although the terms “first”, “second”, etc.may be used herein to describe various elements, components, regions,layers and/or sections, these elements, components, regions, layersand/or sections should not be limited by these terms. These terms areonly used to distinguish one element, component, region, layer orsection from another element, component, region, layer or section. Thus,a first element, component, region, layer or section discussed belowcould be termed a second element, component, region, layer or sectionwithout departing from the teachings of example embodiments.

Spatially relative terms, such as “beneath,” “below,” “lower,” “above,”“upper” and the like, may be used herein for ease of description todescribe one element or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the exemplary term “below” can encompass both anorientation of above and below. The device may be otherwise oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of exampleembodiments. As used herein, the singular forms “a,” “an” and “the” areintended to include the plural forms as well, unless the context clearlyindicates otherwise. It will be further understood that the terms“comprises”, “comprising”, “includes” and/or “including,” if usedherein, specify the presence of stated features, integers, steps,operations, elements and/or components, but do not preclude the presenceor addition of one or more other features, integers, steps, operations,elements, components and/or groups thereof.

Example embodiments are described herein with reference tocross-sectional illustrations that are schematic illustrations ofidealized embodiments (and intermediate structures) of exampleembodiments. As such, variations from the shapes of the illustrations asa result, for example, of manufacturing techniques and/or tolerances,are to be expected. Thus, example embodiments should not be construed aslimited to the particular shapes of regions illustrated herein but areto include deviations in shapes that result, for example, frommanufacturing. For example, an implanted region illustrated as arectangle may have rounded or curved features and/or a gradient ofimplant concentration at its edges rather than a binary change fromimplanted to non-implanted region. Likewise, a buried region formed byimplantation may result in some implantation in the region between theburied region and the surface through which the implantation takesplace. Thus, the regions illustrated in the figures are schematic innature and their shapes are not intended to illustrate the actual shapeof a region of a device and are not intended to limit the scope ofexample embodiments.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which example embodiments belong. Itwill be further understood that terms, such as those defined incommonly-used dictionaries, should be interpreted as having a meaningthat is consistent with their meaning in the context of the relevant artand will not be interpreted in an idealized or overly formal senseunless expressly so defined herein.

Gallium nitride (GaN), as a nitride semiconductor, may be a relativelywide bandgap material with an energy bandgap of about 3.39 eV. Galliumnitride may be a direct transition type material and may be suitable forshort-wavelength light-emitting devices.

Growth of a single crystal of GaN in a liquid phase generally requires arelatively high temperature of at least about 1500° C. and a nitrogenatmosphere of about 20,000 atm to obtain a relatively high nitrogenvapor pressure at the melting point. It may be relatively difficult tomass-produce single crystals of GaN by using a liquid phase growthmethod. The currently available size of the single crystal GaN by thegrowth method in the liquid phase is about 100 mm², which may not belarge enough to be used in fabrication of light-emitting devices. A GaNthin film may also be grown by vapor deposition methods employing aheterogeneous substrate. Such vapor deposition methods may include, forexample, a metal organic chemical vapor deposition (MOCVD) method and ahydride or halide vapor phase epitaxy (HYPE) method. Sapphire may beused for the heterogeneous substrate in fabricating the GaN thin filmbecause sapphire may be relatively stable at relatively high temperatureand also may be relatively inexpensive.

Growing higher quality GaN films on a sapphire substrate may berelatively difficult because of a difference of about 16° A) in latticeconstants and a difference of about 25% in coefficients of thermalexpansion between sapphire substrates and GaN thin films. Due to thesedifferences, there may be a strain on the interface between the sapphiresubstrate and the GaN thin film. The strain may cause lattice defects inthe GaN crystal and/or cracks in the interface, and may result in areduction of the lifespan of a device fabricated on the GaN thin film.The light-emitting efficiency of a light-emitting diode (LED) fabricatedon the sapphire substrate may be limited because of a difference betweenrefractive indexes of the sapphire substrate and the GaN thin film, aswell as, the stress induced defects in the GaN crystal. A substrate withthe same or similar characteristics to a GaN thin film, such as a GaNsubstrate, and fabricating a device on the nitride semiconductorsubstrate (GaN substrate) by a homoepitaxy process, may reduce theoccurrence of these issues.

One or more example embodiments may provide a method of growing anitride semiconductor layer. According to example embodiments, a nitridesemiconductor layer may be grown on a substrate with few and/ordecreased cracks, and/or without cracks by reducing and/or eliminatingthe differences between the lattice constants and/or the thermalexpansion coefficients of the substrate and the nitride semiconductorlayer formed by, for example, an HVPE method. A substrate may beprepared to grow the nitride semiconductor layer. Nitride semiconductordots may be formed on the substrate. The nitride semiconductor dots maybe arranged in a first direction, and may reduce the cracks generateddue to the differences between the lattice constants and/or the thermalexpansion coefficients of the substrate and a nitride semiconductorlayer/film. The nitride semiconductor layer may be grown as a singlecrystal by using the nitride semiconductor dots as cores. Althoughexample embodiments are described with respect to nitride semiconductorlayers, methods of growing semiconductor layers according to exampleembodiments may be widely applied to the growth of a material layer on amaterial layer with different properties (e.g., thermal expansioncoefficients and/or lattice constants).

The vertical and horizontal growth speeds of the nitride semiconductorlayer may be controlled by, for example, adjusting a ratio of a groupIII-V semiconductor material and growth temperature. Because the nitridesemiconductor dots may be formed and arranged in a first direction, thenitride semiconductor layer may be grown as a single crystal. While thenitride semiconductor layer is growing as the single crystal the nitridesemiconductor dots may be connected to each other. During the growth, astress relaxation layer may be formed between the nitride semiconductordots and the nitride semiconductor layer. The stress relaxation layermay be continuously grown with the nitride semiconductor layer at thesame or substantially the same temperature at which the nitridesemiconductor layer is growing. In the stress relaxation layer,dislocations generated on the interfaces between the nitridesemiconductor dots and the nitride semiconductor layer may meet and maybe reduced. The thickness of the stress relaxation layer may correspondto a stress relaxation thickness at which the nitride semiconductor dotsconnect to each other.

The nitride semiconductor layer may be grown to a thickness that isgreater than or equal to a stress relaxation thickness. As an example,the stress relaxation layer may have a thickness of about 40 μm to about50 μm, inclusive. The nitride semiconductor layer may be separated fromthe substrate by using one of commonly known techniques, for example, alaser liftoff method. A freestanding nitride semiconductor substrate maybe obtained by the separation. The freestanding nitride semiconductorsubstrate may include the nitride semiconductor layer and the nitridesemiconductor dots, which may be presented at a surface of the nitridesemiconductor layer. The stress relaxation layer may exist between thenitride semiconductor layer and the nitride semiconductor dots. In thefreestanding nitride semiconductor substrate, the nitride semiconductordots may be of hexagonal shape and may exist on the surface of thenitride semiconductor layer, which initially interfaced with thesubstrate (e.g., sapphire substrate), but separated from the substrate.

According to at least some example embodiments, a relatively thick GaNlayer may be grown on a sapphire substrate by using, for example, a HVPEmethod to fabricate a GaN substrate. The sapphire substrate may be usedas a heterogeneous substrate for growing the relatively thick GaN layer.Sapphire may have a hexagonal structure similarly to GaN, and may berelatively inexpensive and relatively stable at higher temperatures.Sapphire may generate strain at the interface due to the differencesbetween the lattice constants and the thermal expansion coefficients ofGaN and sapphire. The strain may result in lattice defects and/or cracksin the crystal. When a GaN layer is formed on a sapphire substratecracks may be formed in the GaN layer. According to at least someexample embodiments, GaN dots arranged in a first direction may be usedto reduce and/or eliminate the possibility of stress induced crackformation. To obtain a relatively thick GaN layer, GaN may be grown fromthe GaN dots in vertical and horizontal directions. A thickness of therelatively thick GaN layer may be determined based on the average sizeof the GaN dots.

FIG. 1 is a cross-sectional diagram illustrating methods of growing asemiconductor layer on a substrate (10) according to exampleembodiments. FIG. 2 is a cross-sectional diagram illustrating afreestanding semiconductor substrate obtained by separating a relativelythick semiconductor layer (50) from a substrate (10) in the structureshown in FIG. 1. FIG. 3 is a perspective diagram of dots (30) formed ona substrate. The semiconductor layer may be, for example, a nitridesemiconductor layer (e.g., GaN). The substrate (10) may be, for example,a sapphire substrate. The dots (30) may be, for example, nitride dots(e.g., GaN dots).

Referring to FIG. 1, the substrate (10) may be prepared to grow thesemiconductor layer 50. As illustrated in FIG. 3, dots (30) (e.g., GaNsemiconductor dots) may be formed on the substrate (10). The dots (30)may reduce stress induced cracks generated due to differences betweenthe lattice constants and/or the thermal expansion coefficients of thesubstrate (10) and the thick semiconductor layer (50). The dots (30) maybe represented as a dot layer as shown in FIG. 1. According to one ormore example embodiments, in a process to form the dots (30), thesubstrate (10) may be mounted in an HVPE reactor. A halide may begenerated in the reactor. For example, GaCl may be synthesized fromhydrogen chloride (HCl) and gallium (Ga) metal at a relatively hightemperature. The halide may be processed to form dots (30). For example,GaCl may be processed with ammonia (NH₃) to grow GaN dots (30) on asapphire substrate (10).

According to one or more example embodiments, a surface of the substrate(10) may be treated to remove atoms. Seeds may be formed bysubstitutionally filling vacancies generated by the removal of the atomswith at least one type of atom included in a material of the pluralityof seeds. For example, if the semiconductor is GaN, a sapphire substrate(10) mounted in an HVPE reactor may be processed with HCl+NH₃ to removeoxygen from a surface of the sapphire substrate. Nitride seeds (e.g.,nucleation sites) may be formed on the substrate. For example, aluminumnitride (AlN) seeds (not shown) may be formed as seeds on which to growGaN dots (30) on the surface of a sapphire substrate (10). The HCl andGa may react with each other to form GaCl, and the GaCl may react withammonia (NH₃). GaN may be grown from the AlN seeds and the GaN dots (30)may be formed on the sapphire substrate (10). The GaN dots (30) may begrown at relatively high temperatures, for example, about 900° C.Referring to FIG. 3, the nitride dots (30) may have hexagonal shapes andmay be arranged in a given direction, for example, a c-axis direction.Example embodiments are not limited to the use of seeds and GaN dots(30) may be formed directly on the sapphire substrate (10) without theuse of seeds.

According to example embodiments, AlN nano dots may be formed on thesapphire substrate (10) as seeds, and GaN dots (30) may be grown on theAlN nano dots. The AlN nano dots may be part of (e.g., inside) the GaNdots (30). In order to form AlN nano dots on a surface of a sapphiresubstrate (10), NH₃ and HCl may be simultaneously introduced into achamber. Because the surface of the sapphire (Al₂O₃) substrate (10) mayinclude oxygen dangling bonds, some oxygen may be removed by HCl, andthe vacancies (originally occupied by the removed oxygen) may be filledby nitrogen thermally decomposed from NH₃. AlN nano dots may be randomlyformed on the surface of the sapphire substrate (10) according to anoxygen substitution process.

FIG. 4A is a scanning electron microscope (SEM) image of ALN nanodots ona sapphire substrate. Referring to FIG. 4A, the average size of AlN nanodots may be controlled by various parameters including, for example, anamount/(flow rate×time period) of NH₃ and HCl and/or a temperature ofthe sapphire substrate (10). As an example, AlN dots may be formed usinga 3000 sccm flow rate of NH₃ and a 200 sccm flow rate of HCl, at asapphire substrate temperature of about 970° C., for about 5 minutes, ina reactor with a diameter of about 15 cm. The AlN nano dots may berandomly/uniformly formed on a sapphire substrate (10). The average sizeof AlN nano dots may be in the range from about 10 nm to about 100 nm.Sizes and density of AlN nano dots may be determined according totemperature and time period. The average size of GaN dots (30) and athickness of the GaN layer (50) may be a function of the average size ofthe ALN nano dots.

FIGS. 4B and 4C are scanning electron microscope (SEM) images showingGaN dots (30) formed on a sapphire substrate (10). Referring to FIGS. 4Band 4C, the GaN dots (30) may be arranged in a c-axis direction.

The semiconductor layer (50) may be grown on the nitride dots (30). Thenitride dots (30) may act as cores and the semiconductor layer (50) maygrow from the cores. The growing speeds in vertical and horizontaldirections may be controlled by adjusting a ratio of the group III-Vsemiconductor material and/or the growing temperature. Because thehexagonal nitride dots (30) shown in FIGS. 4B and 4C may be arranged inone direction a semiconductor may be grown as a single crystal.

FIG. 5 is an optical microscope image showing a stress buffer layer (40)formed between GaN dots (30) used as cores on a sapphire substrate (10),and a GaN layer (50) on both of the GaN dots (30) and the stress bufferlayer (40). FIG. 5 may show that the stress relaxation layer (40) formedbetween the GaN dots (30) and the GaN layer (50) is formed when the GaNlayer (50) is grown on the sapphire substrate by using the GaN dots (30)as cores. The GaN layer (50) may be grown to a thickness that is aboutgreater than or equal to a stress relaxation layer thickness of a stressrelaxation layer (40) in which the nitride dots (30) are connected toeach other during the growing of the GaN layer (50). The stressrelaxation layer (40) may be formed between the GaN dots (30) and theGaN layer (50) during the growing of the GaN layer (50).

The stress relaxation layer (40) may be continuously grown at the sameor substantially the same temperature as the GaN layer (50). When theGaN layer (50) is grown on the GaN dots (30) dislocations may begenerated at the interfaces of the GaN dots (30). The GaN may be grownfrom each GaN dot/core (30) and connected to each other at a point atwhich the dislocations are partially removed and the stress relaxationlayer (40) is formed. The stress relaxation layer (40) may be grown fromGaN dots (30) formed with/on AlN nano dots formed on a sapphiresubstrate (10) as seeds. AlN nano dots may be inside the GaN dots.According to example embodiments, the stress relaxation layer (40) maybe grown from GaN dots formed directly on the sapphire substrate (10)without employing any seeds and the GaN dots may not include AlN nanodots. The stress relaxation layer (40) may have thickness of about 40 μmto about 50 μm, inclusive, as described above. The thickness of thestress relaxation layer (40) may vary depending on the average size ofthe GaN dots (30). For example, the thickness of the stress relaxationlayer may be from about 1 μm to about 100 μm, inclusive, according tothe average size of the dots (30).

When GaN is grown using GaN dots, most of which have a size of about 0.4μm or greater, a stress relaxation layer thickness (coalescence),according to example embodiments in which the cores contact each other,may be about 40 μm to about 50 μm, inclusive. The thickness of thestress relaxation layer (50) may correspond to the stress relaxationthickness. When the thickness of the GaN layer (50) is about 60 μm toabout 70 μm or greater, the GaN layer (50) may have an almost mirrorsurface and there may be few stress induced cracks. According to exampleembodiments, there may be no stress induced cracks. When the GaN layer(50) is grown to the stress relaxation thickness or greater, the GaNlayer (50) with few or without cracks and/or defects in the crystal maybe obtained with a desired thickness range.

Referring to FIG. 2, a freestanding semiconductor substrate including asemiconductor layer (50) and dots (30) may be obtained by separating thesemiconductor layer (50) with a desired thickness from the substrate(10) with, for example, a laser liftoff method. A relativelyhigh-efficient LED may be fabricated on the freestanding semiconductorsubstrate formed from the nitride dots (30) with few or without stressinduced cracks and defects. The freestanding semiconductor substrate mayinclude a surface which was the initial interface with the sapphiresubstrate (10). The interface may be formed to be an open surfacethrough the separation process. The nitride dots (30) may exist on thesurface of the freestanding GaN layer and may have hexagonal shapes. AnLED may be formed on a side of the freestanding semiconductor substrateopposite the dots (30). The substrate may include a frontside substratelayer including the semiconductor layer (50) and a backside substratelayer including the dots (30).

In a laser liftoff method, a laser beam having a wavelength shorter thanabout 360 nm may be used. For example, semiconductor layer (50) may beirradiated by the laser beam to be separated from the substrate (10).The laser light source for performing the laser liftoff may be, forexample, a third harmonic generation (about 321 nm) of a Nd:YAG laserwith a wavelength of about 1064 nm, a KrF excimer laser having awavelength of about 248 nm and/or a XeCl excimer laser having awavelength of about 330 nm. When the laser beam having a wavelength ofabout 360 nm or shorter is irradiated onto the substrate (10) and thesemiconductor layer (50), the interface between the semiconductor layer(50) and the substrate (10) may absorb the laser beam. For example, ifthe semiconductor layer (50) is GaN and the substrate (10) is sapphire,the GaN at the interface between the semiconductor layer (50) and thesapphire substrate (10) may become Ga+½N², and may cause separation ofthe GaN layer (50) from the sapphire substrate (10).

A stress relaxation layer is not separately shown in FIGS. 1 and 2because the stress relaxation layer may be formed during the growingprocess of the semiconductor layer (50) on the dots (30) up to a desiredthickness. The thickness of the stress relaxation layer may varydepending on the average size of the dots (30). According to exampleembodiments, the stress relaxation layer may not be classified as aseparate layer.

According to methods of growing nitride semiconductor layers of at leastsome example embodiments, a nitride semiconductor may be grown using aHVPE method. When GaN is grown on a sapphire substrate (10) by the HVPEmethod using GaN dots, the GaN dots (30) may be grown in-situ. GrowingGaN on a sapphire substrate (10) with GaN dots (30) may provide arelatively high quality, relatively thick GaN layer (50) with few orwithout cracks and/or defects generated due to the differences betweenthe lattice constants and the thermal expansion coefficients of thesapphire substrate and the GaN.

Referring to FIGS. 4B and 4C, most of the GaN dots (e.g., about 90% ofthe GaN dots) may be a size of about 0.4 μm or less. In FIG. 4C, most ofthe GaN dots (e.g., about 90% of the GaN dots) may be a size of about0.4 μm to about 0.8 μm, inclusive. The GaN dots with a relatively smallaverage size as shown in FIG. 4B may be formed at a relatively lowgrowing temperature, for example, about 980° C. to about 990° C.,inclusive. The GaN dots with a relatively large average size as shown inFIG. 4C may be formed at a relatively high growing temperature, forexample, about 1040° C. The temperature for a desired average size ofGaN dots may be varied during the growing process at differentconditions. An average size of GaN dots may depend upon various factors.In FIGS. 4B and 4C, the GaN dots may be directly formed on the sapphiresubstrate (10) or may be formed after forming the AlN nano dot seeds asshown FIG. 4A on the sapphire substrate (10).

For GaN dots with an average size, for example, of about 0.4 μm or less(as shown in FIG. 4B), a GaN layer grown using the relatively fine sizeof GaN dots as the cores may include a mirror-like surface with athickness of about 10 μm or more. With the relatively fine size of GaNdots, the relatively thin GaN layer having a thickness of about 10 μmmay be obtained. When the GaN dots are of an average size, for example,of about 0.4 μM or more (e.g., about 0.4 μm to about 0.8 μm, inclusive),a GaN layer grown using the relatively coarse size of GaN dots as thecores may be grown up to a relatively large thickness (e.g., about 100μm to about 1000 μm). This relatively thick GaN layer may be used, forexample, as a freestanding GaN substrate for fabricating high and/orimproved efficiency LEDs.

According to methods of growing nitride semiconductor layers accordingto one or more example embodiments, a GaN layer may be grown to athickness of about 300 μm or more (e.g., about 300 μm to about 400 μM,inclusive). When the GaN layer is grown using a relatively coarseaverage size of GaN dots (e.g., about 0.4 μm to about 0.8 μm,inclusive), the GaN layer may have a thick thickness of about 300 μM ormore. This relatively thick GaN layer may be separated from the sapphiresubstrate, and a freestanding GaN substrate with a sufficient thicknessto be a substrate may be obtained and used for fabricating a devicethereon. The GaN layer may be grown to be relatively thin (e.g., athickness of about 300 μm or less) without creating stress inducedcracks and/or defects. A high and/or improved quality GaN layer, as wellas a freestanding GaN substrate, with about any desired thickness may beobtained using the GaN dots according to methods of growingsemiconductor layers according to example embodiments.

When the GaN layer is grown by using the relatively coarse average sizeof GaN dots (e.g., about 0.4 μm or more) as the cores, the stressrelaxation thickness (coalescence), in which the cores are connected toeach other, may be about 40 μm to about 50 μm, inclusive. When the GaNlayer is grown using the relatively coarse average size of GaN dots asthe cores, the GaN layer may change into a mirror-like status withoutforming cracks at a relatively low thickness (e.g., about 60 μm to about70 μM, inclusive). When the thickness of the GaN layer is greater thanor equal to a thickness of the stress relaxation layer (coalescence) ata given average size of the GaN dots, a relatively high quality GaNlayer without cracks and/or defects may be obtained.

FIG. 6 is an optical image showing thick GaN/sapphire layers grownaccording to example embodiments with diameters of about 3 inches andabout 4 inches. The GaN/sapphire structures are grown by using GaN dotsaccording to methods of growing semiconductor layers of exampleembodiments. Referring to FIG. 6, the GaN layer may have little or nocracks.

While example embodiments are particularly shown and described, it willbe understood by one of ordinary skill in the art that variations inform and detail may be made therein without departing from the spiritand scope of the claims. For example, although methods of growingnitride semiconductor layers according to example embodiments isdescribed above with respect to GaN layer growth on a sapphiresubstrate, such should be considered in a descriptive sense only and notfor purposes of limitation. It should be apparent that modifications andvariations thereto are possible, all of which fall within the truespirit and scope of example embodiments. It is to be realized thatoptimum relationships for components and steps, including variations inorder, form, content, function, manner of operation and method offabrication, are deemed readily apparent and obvious to one skilled inthe art, and all equivalent relationships to those illustrated in thedrawings and described in the specification are intended to beencompassed. The above description and drawings are illustrative ofmodifications that can be made without departing from the scope of thisdisclosure, the scope of which is to be limited only by the followingclaims.

Therefore, the foregoing is considered as illustrative only of theprinciples of example embodiments. Further, because numerousmodifications and changes will be made by those skilled in the art, itis not desired to limit example embodiments to the exact constructionand operation shown and described, and accordingly, all suitablemodifications and equivalent are intended to fall within the scope ofthe claims.

1. A method of manufacturing a material layer, the method comprising:forming a seed layer including a plurality of seeds on a first layerincluding a first material; selectively growing a plurality of coresfrom the seeds on the first layer; growing a second layer including atleast one second material from the cores; and growing a third layerincluding at least one third material on the second layer, the firstmaterial different from the third material.
 2. The method of claim 1,wherein there is at least about a 15% difference between latticeconstants and coefficients of thermal expansion of the first and thirdmaterials.
 3. The method of claim 1, wherein the plurality of seedsinclude a first nitride.
 4. The method of claim 3, wherein the pluralityof cores include a second nitride that is different from the firstnitride.
 5. The method of claim 2, wherein the coefficient of thermalexpansion of the first material differs from the coefficient of thermalexpansion of the third material by at least about 25%.
 6. The method ofclaim 2, wherein the third layer is substantially crack free.
 7. Themethod of claim 1, wherein the growing of the plurality of cores and thegrowing of the third layer are performed in-situ.
 8. The method of claim1, wherein the growing of the plurality of cores includes growing theplurality of cores to an average size of greater than or equal to about0.4 μm.
 9. The method of claim 8, wherein the growing of the pluralityof cores includes growing the plurality of cores to an average size ofabout 0.4 μm to about 0.8 μm.
 10. The method of claim 9, wherein thegrowing of the third layer includes growing the third layer to athickness of about 100 μm to about 1000 μm.
 11. The method of claim 1,wherein the growing of the plurality of cores includes growing theplurality of cores to an average size of less than or equal to about 0.4μm.
 12. The method of claim 11, wherein the growing of the third layerincludes growing the third layer to a thickness of less than or equal toabout 10 μm.
 13. The method of claim 4, wherein the growing of theplurality of cores includes growing the plurality of cores into asubstantially hexagonal shape.
 14. The method of claim 1, wherein thefirst layer includes sapphire (Al₂O₃), and the third layer includesgallium nitride (GaN).
 15. The method of claim 1, further comprising:treating a surface of the first layer to remove a plurality of atoms,wherein the forming of the seed layer includes forming the seeds byfilling vacancies formed during the treating of the surface with atleast one type of atom included in a material of the plurality of seeds.16. The method of claim 15, wherein the forming of the seeds includesforming the seeds to an average size of about 10 nm to about 100 nm. 17.The method of claim 1, wherein the growing of the third layer includesgrowing the third material as a single crystal based on a crystalorientation of the cores.
 18. The method of claim 17, wherein thegrowing of the plurality of cores includes growing the plurality ofcores in a c-axis direction.